Secondary Bracing Ligands Drive Heteroleptic Cuboctahedral PdII12 Cage Formation.

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Espinosa, Carles Fuertes 
Nitschke, Jonathan R  ORCID logo

The structural complexity of self-assembled metal-organic capsules can be increased by incorporating two or more different ligands into a single discrete product. Such complexity can be useful, by enabling larger, less-symmetrical, or more guests to be bound. Here we describe a rational design strategy for the use of subcomponent self-assembly to selectively prepare a heteroleptic cage with a large cavity volume (2631 Å3) from simple, commercially available starting materials. Our strategy involves the initial isolation of a tris(iminopyridyl) PdII3 complex 1, which reacts with tris(pyridyl)triazine ligand 2 to form a heteroleptic sandwich-like architecture 3. The tris(iminopyridyl) ligand within 3 serves as a "brace" to control the orientations of the labile coordination sites on the PdII centers. Self-assembly of 3 with additional 2 was thus directed to generate a large PdII12 heteroleptic cuboctahedron host. This new cuboctahedron was observed to bind multiple polycyclic aromatic hydrocarbon guests simultaneously.

3402 Inorganic Chemistry, 3403 Macromolecular and Materials Chemistry, 34 Chemical Sciences
Is Part Of
European Research Council (695009)
Engineering and Physical Sciences Research Council (EP/P027067/1)
EPSRC (EP/T031603/1)